Method of modifying polymers

Patent metadata

Field	Value
Publication number	US-2016145356-A1
Application number	US-201414893751-A
Country	US
Kind code	A1
Filing date	May 26, 2014
Priority date	May 24, 2013
Publication date	May 26, 2016
Grant date	—

Abstract

A method of modifying a polymer having hydroxyl groups, selected from the group of polysaccharides and lignin, to give a modified polymer comprising the step of contacting said polymer with at least one organic phosphonate salt in order to chemically modify the polymer, said organic phosphonate salt being in a liquid phase. The method of polymer modification provides novel polymers. Modified polymers obtained from a polymer having been treated with at least one organic phosphonate salt are also disclosed. The modified polymers can be used as such or separated and optionally recovered from the solution, optionally being formed into particular materials or shapes.

First claim

What is claimed is:

1 . A method of modifying a polymer having hydroxyl groups to give a modified polymer comprising the step of contacting said polymer with at least one organic phosphonate salt in order to chemically modify the polymer, said organic phosphonate salt being in a liquid phase, and wherein the organic phosphonate salts are of Formula III

wherein
R 1 is selected from a hydrogen radical, a linear or branched alkyl radical having 1 to 20 carbon atoms, an aryl radical having 4 to 24 carbon atoms, and R 2 is a cation selected from the group of H + , Li + , Na + , K + , Rb + , Cs + , Fr + , Cu + , Ag + , substituted and unsubstituted ammonium, phosphonium, and sulfonium, and five-membered heterocycles having 1, 2 and 3 heteroatoms and mixtures thereof.

2 . The method according to claim 1 wherein R 2 is a five membered heterocycle selected from a group consisting of methylpyrrolidinium, isothiazolium, isoxazolium, oxazolium, pyrrolium, and thiophenium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, amidinium, guanidinium, phosphazenium, 1-ethyl-3-methylimidazolium, and triazolium.

3 . The method according to claim 1 wherein R 1 is an aryl radical comprising at least one heteroatom selected from O, N and S.

4 . The method according to claim 1 wherein R 1 is an alkyl or aryl radical substituted with 1 to 10 substituents selected from hydroxyl, carboxy, halo, amino, and thio groups.

5 . The method according to claim 1 , wherein the modified polymer contains unreacted hydroxyl groups.

6 . The method according to claim 5 , wherein the ratio of phosphonate groups to hydroxyl groups in the modified polymer is 1000:1 to 1:1000.

7 . The method according to claim 5 , wherein the ratio of phosphonate groups to hydroxyl groups in the modified polymer is 100:1 to 1:100.

8 . The method according to claim 5 , wherein the ratio of phosphonate groups to hydroxyl groups in the modified polymer is 10:1 to 1:10.

9 . The method according to claim 1 , wherein R 2 is an ammonium ion substituted by one or more groups selected from the group of linear or branched alkyl radicals, said alkyl radicals having 1 to 10 carbon atoms or an aryl radical having 5 to 24 carbon atoms.

10 . The method according to claim 1 , wherein the amount of organic phosphonate salt in the liquid phase is between 0.1 and 100.0% of the total weight of the liquid phase.

11 . The method according to claim 1 , wherein the amount of organic phosphonate salt in the liquid phase is between 1.0 and 50.0%, of the total weight of the liquid phase.

12 . The method according to claim 1 , wherein the amount of organic phosphonate salt in the liquid phase is between 2.0 and 20.0% of the total weight of the liquid phase.

13 . The method according to claim 1 , wherein the amount of organic phosphonate salt in the liquid phase is between 8.0 and 12.0%, of the total weight of the liquid phase.

14 . The method according to claim 1 , wherein the polymer is contacted with the phosphonate salt at a molar ratio of hydroxyl groups to phosphonate groups of 1:0.1 to 1:1000.

15 . The method according to claim 1 , wherein the polymer is contacted with the phosphonate salt at a molar ratio of hydroxyl groups to phosphonate groups of 1:0.5 to 1:100.

16 . The method according to claim 1 , wherein the polymer is contacted with the phosphonate salt at a molar ratio of hydroxyl groups to phosphonate groups of 1:1 to 1:50.

17 . The method according to claim 1 , wherein the polymer is modified by chemical reaction between the organic phosphonate salts and hydroxyl groups of the polymer, said chemical reaction giving polymer phosphonates and a weight percent gain (WPG) in the polymer of 0.001-60.000%.

18 . The method according to claim 1 , wherein the polymer is modified by chemical reaction between the organic phosphonate salts and hydroxyl groups of the polymer, said chemical reaction giving polymer phosphonates and a weight percent gain (WPG) in the polymer 1.000-55.000%

19 . The method according to claim 1 , wherein the polymer is modified by chemical reaction between the organic phosphonate salts and hydroxyl groups of the polymer, said chemical reaction giving polymer phosphonates and a weight percent gain (WPG) in the polymer 5.000-50.000%.

20 . The method according to claim 1 , wherein the polymer is modified by chemical reaction between the organic phosphonate salts and hydroxyl groups of the polymer, said chemical reaction giving polymer phosphonates and a weight percent gain (WPG) in the polymer 10.000-40.000%.

21 . The method according to claim 1 , wherein the polymer is selected from polysaccharides and lignin.

22 . A polymer obtained by a method according to claim 1 .

23 . The polymer according to claim 22 , wherein the polymer is selected from polysaccharides and lignin.

24 . The polymer according to claim 23 , further comprising hydroxyl groups, and wherein the ratio of phosphonate groups to hydroxyl groups being 1000:1 to 1:1000.

25 . The polymer according to claim 23 , further comprising hydroxyl groups, and wherein the ratio of phosphonate groups to hydroxyl groups being, 100:1 to 1:100.

26 . The polymer according to claim 23 , further comprising hydroxyl groups, and wherein the ratio of phosphonate groups to hydroxyl groups being 10:1 to 1:10.

27 . The polymer according to claim 22 , wherein the polymer is provided in the form of fibres or filaments.

28 . Spun fibres comprising a polymer according to claim 22 .

29 . A thin film comprising a polymer according to claim 22 .

30 . The thin film according to claim 29 exhibiting properties of oxygen barrier.

31 . A polymer solution comprising a polymer according to claim 22 dissolved or dispersed in a liquid phase.

32 . The polymer solution according to claim 31 , wherein the liquid phase comprises a polar solvent.

33 . The polymer solution according to claim 31 , wherein the polar solvent comprises water.

34 . The polymer solution according to claim 31 , wherein the concentration of the polymer in the liquid phase is 0.1 to 20% by weight, calculated from the total weight of the solution.

Assignees

• Stora Enso Oyj
• Metsä Fibre Oy

Inventors

• King Alistair W T
• Selg Christoph
• Karhunen Pirkko
• Matikainen Jorma
• Kilpeläinen Ilkka

Classifications

• C08L1/02

  Cellulose; Modified cellulose · CPC title

• C08B37/003 Primary

  Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof · CPC title

• C08B5/00

  Preparation of cellulose esters of inorganic acids {, e.g. phosphates (rendering cellulose suitable for esterification C08B1/02)} · CPC title

• C07K14/415

  from plants · CPC title

• C08L97/02

  Lignocellulosic material, e.g. wood, straw or bagasse {(manufacture of articles made from lignocellulosic material by dry processes B27N)} · CPC title